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United States Patent |
5,183,886
|
Takagishi
|
February 2, 1993
|
Process for preparation of crystalline oxytitanium phthalocyanine
showing A,B or C form
Abstract
A process for the preparation of crystalline oxytitanium phthalocyanine
comprising contacting dichlorotitanium phthalocyanine, dibromotitanium
phthalocyanine or a mixture of them with at least one organic solvent
selected from the group consisting of aromatic nitro compounds,
nitrogen-containing cyclic ethers, aromatic amines, alcohols containing
not less than 4 carbon atoms, aldehydes, ketones, lactones, lactams, acid
amides, nitriles, alkyl sulfoxides, substituted phenols and
non-substituted phenols in association with water.
Inventors:
|
Takagishi; Iwao (Yokohama, JP)
|
Assignee:
|
Mitsubishi Kasei Corporation (Tokyo, JP)
|
Appl. No.:
|
888246 |
Filed:
|
May 22, 1992 |
Foreign Application Priority Data
| May 22, 1989[JP] | 1-128426 |
| Jul 18, 1989[JP] | 1-185075 |
| Jul 27, 1989[JP] | 1-194815 |
Current U.S. Class: |
540/141; 540/142; 540/143 |
Intern'l Class: |
C09B 067/50 |
Field of Search: |
540/141
|
References Cited
U.S. Patent Documents
4664997 | May., 1987 | Suzuki et al. | 430/58.
|
4725519 | Feb., 1988 | Suzuki et al. | 430/58.
|
4775251 | Oct., 1988 | Tanaka et al. | 540/143.
|
4777251 | Oct., 1988 | Tanaka et al. | 540/143.
|
4777257 | Oct., 1988 | Kanao | 546/342.
|
Foreign Patent Documents |
61-217050 | Sep., 1986 | JP.
| |
62-256866 | Nov., 1987 | JP.
| |
62-256867 | Nov., 1987 | JP.
| |
63-366 | Jan., 1988 | JP.
| |
63-000366 | Jan., 1988 | JP.
| |
63-20365 | Jan., 1988 | JP.
| |
Other References
CA:108 (16): 133405f (1988).
CA 108 (16): 133406g (1988).
CA 108 (16): 133407h (1988).
|
Primary Examiner: Bond; Robert T.
Assistant Examiner: Venkat; Jyoihsna
Attorney, Agent or Firm: Conlin; David G., Buckley; Linda M., Corless; Peter F.
Parent Case Text
This is a continuation of copending application Ser. No. 07/526,585 filed
on May 21, 1990 now abandoned.
Claims
What is claimed is:
1. A process for the preparation of crystalline oxytitanium phthalocyanine
showing A, B or C crystalline form consisting of contacting
dichlorotitanium phthalocyanine, dibromotitanium phthalocyanine or a
mixture of them with at least one organic solvent selected from the group
consisting of aromatic nitro compounds, nitrogen-containing cyclic ethers,
aromatic amines, alcohols containing not less than 4 carbon atoms,
aldehydes, ketones, lactones, lactams, acid amides, nitriles, alkyl
sulfoxides and substituted phenols to produce the crystalline oxytitanium
phthalocyanine.
2. The process as defined in claim 1, wherein the starting material is
dichlorotitanium phthalocyanine.
3. The process as defined in claim 1, wherein the starting material is
dichlorotitanium phthalocyanine, dibromotitanium phthalocyanine or a
mixture of them obtained by the reaction of o-phthalodinitrile with
titanium tetrachloride, titanium tetrabromide or a mixture of them.
4. The process as defined in claim 1, wherein the contact of
dichlorotitanium phthalocyanine, dibromotitanium phthalocyanine or a
mixture of them with the solvent is carried out by mixing them under
agitation.
5. The process as defined in claim 1, wherein dichlorotitanium
phthalocyanine, dibromotitanium phthalocyanine or a mixture of them is
contacted with the solvent at a temperature of from 50.degree. to
200.degree. C.
6. The process as defined in claim 1, wherein the contact is carried out in
a weight ratio of dichlorotitanium phthalocyanine, dibromotitanium
phthalocyanine or a mixture of them to the organic solvent of from 1:5 to
1:100.
7. The process as defined in claim 1, wherein dichlorotitanium
phthalocyanine, dibromotitanium phthalocyanine, or a mixture of them is
contacted with at least one solvent selected from the group consisting of
N-alkyllactams, aromatic nitro compounds, halogenated phenols, aromatic
acid amides, nitrogen-containing cyclic ethers and aromatic primary
amines.
8. The process as defined in claim 1, wherein dichlorotitanium
phthalocyanine, dibromotitanium phthalocyanine or a mixture of them is
contacted with at least one solvent selected from the group consisting of
alcohols containing not less than 4 carbon atoms, aldehydes, ketones,
lactones, lactams (other than N-alkyllactams), non-aromatic acid amides,
substituted phenols (other than halogenated phenols), nitriles, N-alkyl
substituted anilines and alkyl sulfoxides.
9. The process as defined in claim 1, wherein the crystalline oxytitanium
phthalocyanine is further treated with a solvent.
10. The process as defined in claim 1, wherein the crystalline oxytitanium
phthalocyanine is washed.
11. The process as defined in claim 1, wherein the crystalline oxytitanium
phthalocyanine is filtered.
12. The process as defined in claim 11, wherein the filtered crystalline
oxytitanium phthalocyanine is further treated with a solvent.
13. The process as defined in claim 11, wherein the filtered crystalline
oxytitanium phthalocyanine is washed.
14. The process as defined in claim 1, wherein the contact is carried out
in the air.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a process for the preparation of oxytitanium
phthalocyanine (abbreviated as "TiOPc" hereinafter). More precisely, it
relates to a process for the preparation of crystalline TiOPc using
dichlorotitanium phthalocyanine and/or dibromotitanium phthalocyanine as a
starting material.
2. Description of the Prior Art
Phthalocyanines have been well known as a useful material for the
electronic industry as well as a coloring material for paint, printing
ink, resin material and the like, and they are widely used as a material
for electrophotographic photoreceptor.
During our investigation of preparation methods of TiOPc, we found TiOPc
showing major diffraction peaks at Bragg angles (2.theta..+-.0.2.degree.)
of 9.3.degree., 10.6.degree., 13.2.degree., 15.2.degree., 20.8.degree. and
26.3.degree. (designated as "A-type TiOPc" hereinafter), TiOPc showing
major diffraction peaks at Bragg angles (2.theta..+-.0.2.degree.) of
7.6.degree., 10.2.degree., 22.3.degree., 25.3.degree. and 28.6.degree.
(designated as "B-type TiOPc" hereinafter) and TiOPc showing major
diffraction peaks at Bragg angles (2.theta..+-.0.2.degree.) of
7.0.degree., 15.6.degree., 23.4.degree. and 25.6.degree. (designated as
"C-type TiOPc" hereinafter) in their X-ray diffraction spectra and
proposed the production methods for those TiOPc's (Japanese Patent
Application Laying-open Nos. 62-256865, 62-256867 and 63-366).
However, those prior methods require precise adjustments of the parameters
such as the temperature elevation rate during the reaction of
o-phthalodinitrile and titanium tetrachloride and the filtration
temperature after the reaction, and the products of those methods tend to
contain two or more TiOPc crystalline forms.
Japanese Patent Application Laying-open No. 61-217050 discloses a method
for the preparation of TiOPc wherein dichlorotitanium phthalocyanine
(abbreviated as "TiCl.sub.2 Pc" hereinafter) is heated with concentrated
aqueous ammonia and washed with acetone to obtain TiOPc. However, the
product of this method also tends to contain the both of A-type and B-type
crystals of TiOPc, and it requires laborious operation.
Further, this prior method involves further drawbacks because of the use of
TiCl.sub.2 Pc as the starting material. That is, TiCl.sub.2 Pc is produced
by a condensation reaction, of o-phthalodinitrile and titanium chloride
and a hydrolysis of the condensation product with water or aqueous ammonia
according to the following scheme;
##STR1##
however, the hydrolysis of this process requires a lot of time and the
crystallinity of the produced TiOPc is relatively low. Therefore, the
prior methods using TiCl.sub.2 Pc such as described above are extremely
time-consuming and usually require a further physical or chemical
treatment such as a treatment with N-methylpyrrolidone, acetone and the
like.
On the other hand, a method for the production of TiOPc showing a specific
crystalline form by means of a physical treatment had been also proposed
in Japanese Patent Application Laying-open No. 64-17066. This patent
document discloses a method for the production of TiOPc showing the most
distinct diffraction peak at a Bragg angle (2.theta..+-.0.2.degree.) of
27.3.degree. and other peaks at 9.7.degree. and 24.1.degree. (designated
as "D-type TiOPc" hereinafter), wherein TiOPc is ground with polyethylene
glycol by means of a sand grinder and then treated with diluted sulfuric
acid to cause a crystalline transition. However, this method also requires
precise adjustments of the conditions such as the agitating conditions
during the grinding, and the product also tend to contain two crystalline
forms of TiOPc.
The object of the present invention is, therefore, to provide a novel
method capable of eliminating the drawbacks of the prior methods described
above and selectively producing TiOPc showing a specific crystalline form
of A, B, C or D-type.
SUMMARY OF THE INVENTION
Surprisingly, it was found that TiOPc could be easily prepared from
TiCl.sub.2 Pc and/or dibromotitanium phthalocyanine (abbreviated as
"TiBr.sub.2 Pc" hereinafter) in a manner different from the well-known
hydrolysis method.
Therefore, the present invention is a process for the preparation of
crystalline oxytitanium phthalocyanine comprising contacting TiCl.sub.2 Pc
and/or TiBr.sub.2 Pc with at least one organic solvent selected from the
group consisting of aromatic nitro compounds, nitrogen-containing cyclic
ethers, aromatic amines, alcohols containing not less than 4 carbon atoms,
aldehydes, ketones, lactones, lactams, acid amides, nitriles, alkyl
sulfoxides, substituted phenols and non-substituted phenols in association
with water.
According to the process of the invention, crystalline TiOPc showing a
desired crystalline form of A, B, C or D-type can be selectively and
easily produced by suitably selecting the organic solvent to be contacted
with TiCl.sub.2 Pc and/or TiBr.sub.2 Pc. The TiOPc prepared according to
the present invention does not contain undesired contaminative crystalline
form, which is usually found in the TiOPc obtained by any of the prior
processes. Further, the TiOPc obtained by the present invention has a
sufficient degree of crystallinity for any practical use as it is, though
it may be of course further purified by treating with a solvent such as
water, methanol, acetone, N-methylpyrrolidone, dimethyl sulfoxide and
N,N-dimethylformamide.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 to 4 are the X-ray diffraction spectra obtained for the crystalline
TiOPc's in powder form produced in Examples 1, 2, 3 and 27, respectively.
FIG. 5 and FIG. 6 are the X-ray diffraction spectra obtained for the
products in powder form obtained in Comparative Examples 4 and 5,
respectively.
FIGS. 7 to 9 are the X-ray diffraction spectra obtained for the crystalline
TiOPc's in powder form produced in Examples 33, 34 and 37, respectively.
DETAILED DESCRIPTION OF THE INVENTION
The organic solvents used for the present invention include aromatic nitro
compounds, nitrogen-containing cyclic ethers, aromatic amines, alcohols
containing not less than 4 carbon atoms, aldehydes, ketones, lactones,
lactams, acid amides, nitriles, alkyl sulfoxides, substituted phenols and
non-substituted phenols.
The "non-substituted phenol" according to the invention means mono- or
polyfunctional phenols having no substituent other than hydroxyl group(s)
on the benzene ring such as phenol, catechol, resorcin, hydroquinone and
pyrogallol. The "substituted phenols" means phenols having one or more
substituents such as alkyl group and amino group on the benzene ring.
The organic solvent may be either in liquid form or in solid form at the
atmospheric temperature so long as it can take liquid form when it is
contacted with TiCl.sub.2 Pc and/or TiBr.sub.2 Pc. When a solvent having a
high melting point such as phenols is used, it may be melted or mixed with
up to 80%, preferably up to 70% of an inert solvent having a low melting
point which may be selected from ethers, esters, hydrocarbons and the like
to improve the treatability thereof.
The solvents producing A-type and B-type of TiOPc are classified in Tables
1 and 2 below, though there may be some exceptions for each of the
solvents generically mentioned.
TABLE 1
______________________________________
Organic solvents producing A-type TiOPc
Type of Solvent Specific Examples
______________________________________
N-Alkyllactams N-Methylpyrrolidone,
N,N-dimethylimidazolidine-2-one
Aromatic nitro compounds
Nitrobenzene, 1.4-dinitrobenzene
Halogenated phenols
4-Chlorophenol, 2-bromophenol
Acid amides containing
N-Methylformanilide,
aromatic ring N-phenylformanilide
Nitrogen-containing
Morpholine
cyclic ethers
Aromatic primary amines
Aniline, 1,4-diaminobenezene
______________________________________
TABLE 2
______________________________________
Organic solvents producing B-type TiOPc
Type of Solvent Specific Examples
______________________________________
Alcohols containing not
Butanol, pentanol, hexanol,
less than 4 carbon atoms
heptanol, octanol, cyclopentanol,
cyclohexanol, benzyl alcohol,
.beta.-phenylethyl alcohol
Aldehydes n-Butyl aldehyde,
p-butoxybenzaldehyde
Ketones Acetonylacetone, cyclohexanone,
acetophenone
Lactones .gamma.-Butyrolactone
Lactams .epsilon.-Caprolactam
(other than N-alkyllactams)
Non-aromatic acid amides
N,N-Dimethylformamide,
N,N-dimethylacetamide
Substituted phenols
p-Methoxyphenol, p-aminophenol,
(other than halogenated
p-tert-octylphenol, bisphenol A
phenols)
Nitriles Malononitrile
N-Alkyl substituted
N-Ethylaniline
anilines
Alkyl sulfoxides
Dimethyl sulfoxide
______________________________________
The solvents giving C-type TiOPc include 2,5-xylenol.
For obtaining D-type TiOPc, the non-substituted phenols are used in
association with water.
The conditions for the contact of the organic solvent with TiCl.sub.2 Pc
and/or TiBr.sub.2 Pc are not particularly limited insofar as the TiOPc
crystals may be produced.
The temperature for the contact may be selected freely; however, it is
generally selected from the rage of 50.degree. to 200.degree. C. From the
viewpoint of the process efficiency, it is desirable that the temperature
is as high as possible since the higher temperature gives higher
production rate of TiOPc. Therefore, it is advantageous to select a
solvent having a high boiling point.
The duration of the contact may vary depending on the crystalline type to
be produced, the amount of the solvent and the temperature. For example,
when the temperature is 130.degree. C., the contact is generally carried
out for 1 to 3 hours.
The weight ratio of TiCl.sub.2 Pc and/or TiBr.sub.2 Pc to the solvent is
not particularly limited; however, it is preferably selected from the
range of 1:5 to 1:100 from the viewpoint of the efficiency of the contact
and the treatability of the mixture. Too small amount of the organic
solvent would give a poor contact efficiency and thereby resulting a low
production rate of TiOPc.
The method for the contact of TiCl.sub.2 Pc and/or TiBr.sub.2 Pc with the
organic solvent is not also particularly limited, and it may be carried
out by any method so long as the contact of the materials is ensured. For
example, it may be carried out by passing the organic solvent through a
column filled with TiCl.sub.2 Pc and/or TiBr.sub.2 Pc; however it is
preferably carried out by mixing them in an agitation vessel. When the
contact is carried out with an organic solvent containing no oxygen atom
in the molecular structure such as aniline in the absence of oxygen, for
example, in nitrogen atmosphere, the TiOPc crystals can not be produced.
Therefore, the contact with such type of the solvent should be carried out
in an oxygen-containing atmosphere such as in the air. On the other hand,
when the contact is carried out with an organic solvent containing oxygen
as the most of the solvents suitable for the invention, the TiOPc crystals
can be produced in the absence of oxygen. Consequently, it is preferred
that the contact is carried out in the air regardless of the type of the
solvent from the viewpoint of the process economy.
As described above, D-type TiOPc may be produced by using the
non-substituted phenols in association with water. That is, it can be
produced by contacting TiCl.sub.2 Pc and/or TiBr.sub.2 Pc a) with the
non-substituted phenols containing water, or b) with the non-substituted
phenols and subsequently with water.
The conditions for the contact of the TiCl.sub.2 Pc and/or TiBr.sub.2 Pc
with the non-substituted phenols containing water in the method a) above
or with the non-substituted phenols in the method b) above may be similar
to those used for the contact with the other organic solvents. The weight
ratio of the phenols to water in the mixture of phenols and water is
preferably selected from the range of 1:0.01 to 1:100, particularly 1:0.05
to 1:50.
The conditions for the contact with water in the method b) above are not
also particularly limited: however, it is preferably carried out by adding
water to the intermediate product obtained from the treatment of
TiCl.sub.2 Pc and/or TiBr.sub.2 Pc with the phenols and mixing them by
mechanical agitation. The amount of water to be added may be generally 5
to 200 times, particularly, 10 to 100 times by weight of the intermediate
product, and the temperature for the treatment is generally selected from
the range of 20.degree. to 100.degree. C., preferably 50.degree. to
100.degree. C. The duration for the treatment may vary depending on the
temperature. For example, it is generally carried out for 0.5 to 3 hours
at the temperature of 100.degree. C.
The methods a) and b) above may be variably modified insofar as the
production of TiOPc crystals, the purpose of the present invention, is
ensured. For example, it may be modified by supplementing other pre-
and/or aftertreatments as well as optional treatments in the midst of the
process or by using the non-substituted phenols mixed with a material
other than water such as aromatic hydrocarbons.
Such possible and preferred modifications of the process include:
1) TiCl.sub.2 Pc and/or TiBr.sub.2 Pc are contacted with the
non-substituted phenols, water and a mixture of aromatic hydrocarbon and
water successively,
2) TiCl.sub.2 Pc and/or TiBr.sub.2 Pc are contacted with the
non-substituted phenols and subsequently with a mixture of aromatic
hydrocarbon and water, and
3) TiCl.sub.2 Pc and/or TiBr.sub.2 Pc are contacted with the
non-substituted phenols containing water and subsequently with a mixture
of aromatic hydrocarbon and water.
The use of the non-substituted phenols containing water enables the easier
recovery of the obtained TiOPc as compared with the case using the
non-substituted phenol alone since TiOPc shows poor solubility in water.
The weight ratio of the aromatic hydrocarbon to water in the mixture of
them may be selected from the range of 1:0.5 to 1:200, preferably 1:1 to
1:100. Though the weight ratio of the intermediate and the mixture of the
aromatic hydrocarbon and water is not particularly limited, it is
generally selected from the range of 1:5 to 1:200, preferably 1:10 to
1:100. The treatment temperature may be 20.degree. to 100.degree. C.,
preferably 50.degree. to 100.degree. C., and the treatment duration may be
preferably 0.1 to 3 hours. The type of the aromatic hydrocarbon is not
also particularly limited and it may have substituents such as halogen in
the molecular structure thereof; however, it is preferably a solvent
having a melting point of not more than 100.degree. C. for the ease of
mixing with water.
It is noted that the successive or subsequent contact is carried out either
continuously or after the solvent used in the front step is removed.
As described above, the novel process for the preparation of TiOPc
according to the present invention enables to selectively produce TiOPc
having a desired specific crystalline form by an extremely simple process
as compared with any prior method, and therefore it is extremely
advantageous for the production of TiOPc in an industrial scale.
EXAMPLES
This invention is further illustrated more specifically by referring to the
following Examples, but they do not limit the scope of the invention since
the scope of the invention is defined by the appended claims.
Synthesis of TiCl.sub.2 Pc
Into a 2-liter reaction flask equipped with a thermometer, agitator and
reflux condenser, 184 g (0.718 moles) of o-phthalodinitrile and 1,200 ml
of .alpha.-chloronaphthalene were introduced, added with 40 ml (0.364
moles) of titanium tetrachloride under agitation and heated to 200.degree.
C. to react for 5 hours. After cooling the reaction mixture to 120.degree.
C., it was filtered while it was hot to obtain a crude cake of TiCl.sub.2
Pc, which was washed with 1,000 ml of .alpha.-chloronaphthalene to obtain
a blue wet cake of crude TiCl.sub.2 Pc weighing 224 g.
The result of the elemental analysis of the product (in dry state) is shown
below.
______________________________________
C H N Cl
______________________________________
Calcd. % 60.88 2.55 17.75
11.23
Anal. % 60.66 2.37 17.68
11.08
______________________________________
EXAMPLE 1
Into a 200-ml reaction flask equipped with a thermometer, agitator and
reflux condenser, 11.2 g of TiCl.sub.2 Pc wet cake and 150 ml of
N-methylpyrrolidone were introduced, heated to 140.degree. C. and
maintained at the temperature under agitation for 2 hours. After cooling
the reaction mixture to 80.degree. C., it was filtered to obtain a cake,
which was washed with methanol and dried to obtain 7.2 g of blue powder of
A-type TiOPc. Yield: 70% (based on the starting o-phthalodinitrile).
The X-ray diffraction spectrum of the obtained TiOPc in powder form is
shown as FIG. 1.
EXAMPLES 2 TO 26 AND COMPARATIVE EXAMPLES 1 TO 3
TiOPc's were produced by repeating the procedure of Example 1 using various
organic solvents and treatment conditions.
The organic solvents and the treatment conditions employed and the results
are summarized in Table 3 below.
TABLE 3
__________________________________________________________________________
Product
Treatment conditions
(TiOPc)
Temperature
Duration
Yield
Crystal
Example No.
Organic solvent (.degree.C.)
(hr) (g) form
__________________________________________________________________________
2 CH.sub.3 (CH.sub.2).sub.2 CHO
76 3 8.2 B
3
##STR2## 130 2 6.8 C
4
##STR3## 120 3 7.7 A
5
##STR4## 150 1 7.1 A
6
##STR5## 150 2 7.2 A
7
##STR6## 140 2 6.8 A
8
##STR7## 140 2 6.6 A
9
##STR8## 120 2.5
7.8 A
10
##STR9## 140 2 6.9 A
11
##STR10## 140 2 7.1 A
12
##STR11## 140 2 7.2 B
13 CH.sub.3 CO(CH.sub.2).sub.2 COCH.sub.3
140 2 7.5 B
14
##STR12## 140 2 7.1 B
15
##STR13## 130 2 7.7 B
16
##STR14## 130 2 7.2 B
17
##STR15## 130 2 7.1 B
18
##STR16## 130 2 7.2 B
19 CNCH.sub.2 CN 130 2 7.4 B
20
##STR17## 130 2 7.3 B
21
##STR18## 140 2 7.5 B
22
##STR19## 130 2 8.1 B
23
##STR20## 130 2 7.2 B
24
##STR21## 130 2 7.3 B
25
##STR22## 130 2 7.0 B
26
##STR23## 130 2 7.8 B
Comparative Example 1
##STR24## 110 5 No production of TiOPc
Comparative
(CH.sub.3 OCH.sub.2 CH.sub.2).sub.2 O
140 4 No production
Example of TiOPc
Comparative
H.sub.5 C.sub.2 OOC(CH.sub.2).sub.4 COOC.sub.2 H.sub.5
140 4 No production
Example of TiOPc
__________________________________________________________________________
The X-ray diffraction spectra of TiOPc's obtained in Examples 2 and 3 are
shown as FIGS. 2 and 3, respectively.
EXAMPLE 27
Into a 1-liter reaction flask equipped with a thermometer, agitator and
reflux condenser, 110 g of wet cake of TiCl.sub.2 Pc obtained as same as
above and 600 ml n-butanol were introduced and refluxed at 118.degree. C.
under agitation for 2 hours to obtain 75 g (dry weight) of blue crystals
of B-type TiOPc. Yield: 73% (based on the starting o-phthalodinitrile).
The product showed characteristic diffraction peaks at Bragg angles
(2.theta..+-.0.2.degree.) of 7.6.degree., 10.2.degree., 22.3.degree.,
25.3.degree. and 28.6.degree. in the X-ray diffraction spectrum thereof
shown as FIG. 4.
The result of the elemental analysis of the product is shown below.
______________________________________
C H N
______________________________________
Calcd. % 66.68 2.80 19.44
Anal. % 66.40 2.59 19.23
______________________________________
EXAMPLES 28 TO 32 AND COMPARATIVE EXAMPLES 4 AND 5
TiOPc's were produced by repeating the procedure of Example 27 using the
various alcohols and the reaction conditions indicated in Table 4 below.
The results are also shown in Table 4.
TABLE 4
__________________________________________________________________________
Treatment conditions
Product (TiOPc)
Temperature
Duration
Yield
Diffraction
Example No.
Alcohol (.degree.C.)
(hr) (g) Spectrum*
__________________________________________________________________________
28 (CH.sub.3).sub.3 COH
82 3 78 Similar to
FIG. 4
29 CH.sub.3 (CH.sub.2).sub.4 OH
138 2 77 Similar to
FIG. 4
30 CH.sub.3 (CH.sub.2).sub.3 CH(C.sub.2 H.sub.5)CHOH
150 2 71 Similar to
FIG. 4
31
##STR25## 150 2 67 Similar to FIG. 4
32
##STR26## 150 2 73 Similar to FIG. 4
Comparative
CH.sub.3 OH 65 5 84 FIG. 5
Example 4
Comparative
(CH.sub.3).sub.2 CHOH
82 3 81 FIG. 6
Example 5
__________________________________________________________________________
*X-ray diffraction spectra of the products in powder form
Judging from the X-ray diffraction spectra, the product of Comparative
Example 4 is considered to be mainly composed of TiCl.sub.2 Pc, and the
product of Comparative Example 5 is considered to be composed of TiOPc
containing two or more crystalline forms.
EXAMPLE 33
Into a 200-ml Erlenmeyer flask, 11.2 g of wet cake of TiCl.sub.2 Pc
obtained as same as above and 150 g of phenol were introduced, heated to
110.degree. C. and maintained at the temperature under agitation for 5
hours. Then the resulted product was taken by filtration at 50.degree. C.
and washed with 100 ml of methanol. The obtained cake was added with 100
ml of water, agitated for 1 hour at 90.degree. to 100.degree. C. and taken
by filtration. Then, the product was added with 20 ml of o-dichlorobenzene
and 150 ml of water and agitated for 1 hour at 60.degree. C. After
removing the aqueous layer, the organic layer was washed with methanol and
dried to obtained 6.2 g of blue D-type TiOPc powder.
The result of the elemental analysis of the product is shown below.
______________________________________
C H N
______________________________________
Calcd. % 66.68 2.80 19.44
Anal. % 66.88 2.81 19.61
______________________________________
The X-ray diffraction spectrum of the product in powder form is shown as
FIG. 7.
EXAMPLE 34
The procedure of Example 33 was repeated except that the treatment with the
mixture of o-dichlorobenzene and water was omitted to obtain 6.4 g of blue
D-type TiOPc powder.
The result of the elemental analysis of the product is shown below.
______________________________________
C H N
______________________________________
Calcd. % 66.68 2.80 19.44
Anal. % 66.49 2.83 19.31
______________________________________
The X-ray diffraction spectrum of the product in powder form is shown as
FIG. 8.
EXAMPLE 35
The procedure of Example 33 was repeated except that the treatment with
water was omitted to obtain 6.5 g of blue D-type TiOPc powder.
The result of the elemental analysis of the product is shown below.
______________________________________
C H N
______________________________________
Calcd. % 66.68 2.80 19.44
Anal. % 66.67 2.83 19.41
______________________________________
The X-ray diffraction spectrum of the product in powder form was similar to
that of the product of Example 33.
EXAMPLE 36
The procedure of Example 33 was repeated except that the phenol was
replaced by phenol containing 10% of water and that the treatment with
water was omitted to obtain 7.0 g of blue D-type TiOPc powder.
The result of the elemental analysis of the product is shown below.
______________________________________
C H N
______________________________________
Calcd. % 66.68 2.80 19.44
Anal. % 66.50 2.69 19.29
______________________________________
The X-ray diffraction spectrum of the product in powder form was similar to
that of the product of Example 33.
EXAMPLE 37
The procedure of Example 33 was repeated except that the phenol was
replaced by phenol containing 20% of water and that the treatment with the
mixture of water and the aromatic compound was omitted to obtain 7.2 g of
blue D-type TiOPc crystals.
The result of the elemental analysis of the product is shown below.
______________________________________
C H N
______________________________________
Calcd. % 66.68 2.80 19.44
Anal. % 66.51 2.70 19.26
______________________________________
The X-ray diffraction spectrum of the product in powder form is shown as
FIG. 9.
EXAMPLES 38 TO 43 AND COMPARATIVE EXAMPLE 6
TiOPc's were produced by repeating the procedure of Example 33 except that
the various phenols and aromatic compounds shown in Table 5 below were
used and that the reaction conditions were varied as indicated in the
same.
The results are also shown in Table 5.
TABLE 5
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Product
Treatment conditions (TiOPc)
Temperature
Duration
Aromatic Yield
Crystal
Example No.
Phenol (.degree.C.)
(hr) Hydrocarbon (%) form
__________________________________________________________________________
38
##STR27## 130 3
##STR28## 6.8 D
39
##STR29## 140 2
##STR30## 7.1 D
40
##STR31## 110 5
##STR32## 7.3 D
41*
##STR33## 110 5
##STR34## 7.2 D
42
##STR35## 130 3
##STR36## 6.9 D
43
##STR37## 130 3
##STR38## 6.6 D
Comparative Example 6
(CH.sub.3 OCH.sub.2 CH.sub.2).sub.2 O 150 g
130 3
##STR39## No production of
__________________________________________________________________________
TiOPc
*The treatment with water was ommited in Example 41
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